Mono azo pyrazolyl containing dyestuffs

ABSTRACT

AZO DYESTUFFS FREE OF SULPHONIC ACID GROUPS AND HAVING THE FORMULA:   1-(A-N=N-((R-)M-1,4-PHENYLENE)-N(-R1)-CH2-CH(-R2)-),3-R3,   4-R4,5-R5-PYRAZOLE OR   1-(A-N=N-((R-)M-1,4-PHENYLENE)-N(-R1)-CH2-CH(-R2)-),2-R6,   3-R3,4-R4,5-R5-PYRAZOL-2-IUM X(-)   WHEREIN A IS A DIAZO COMPONENT; R IS A NONIONIC SUBSTITUENT; R1 IS H, ALIPHATIC, ARALIPHATIC, OR AROMATIC; R2 IS H OR METHYL; R3, R4, AND R5 ARE H, ALKYL, ARYL, OR ARALKYL; R4 MAY ALSO BE CARBOALKOXY; R6 IS ALKYL OR BENZYL; AND M IS 0, 1, OR 2. THESE DYESTUFFS ARE USEFUL IN THE DYEING OR PRINTING OF FIBROUS MATERIALS, DYESTUFFS (II) PARTICULARLY FOR THOSE BASED OF POLYMERS OR COPOLYMERS OR ACRYLONITRILE AND DICYANO-ETHYLENE AND DYESTUFFS (I) PARTICULARLY FOR THOSE OF AROMATIC POLYESTERS. PROCESS FOR PREPARING THE ABOVE DYESTUFF BY COMBINING A-NH2 WITH A COUPLING COMPONENT HAVING THE FORMULA:   1-(((R-)M-PHENYL)-N(-R1)-CH2-CH(-R2)-),3-R3,4-R4,5-R5-   PYRAZOLE OR   1-(((R-)M-PHENYL)-N(-R1)-CH2-CH(-R2)-),2-R6,3-R3,4-R4,   5-R5-PYRAZOL-2-IUM   WHERE ALL SUBSTITUENT GROUPS HAVE THE ABOVE MEANINGS. PROCESS FOR PREPARING THE QUATERNARY SALT AZO DYESTUFF BY REACTING (I) WITH QUATERNIZING AGENT R6X.

United States Patent ()fice 3,583,970 Patented June 8, 1971 Int. (:1.C09d 29738,- D06p 1/02 US. Cl. 260-163 2 Claims ABSTRACT OF THEDISCLOSURE Azo dyestuffs free of sulphonic acid groups and having theformula:

wherein A is a diazo component; R is a nonionic substituent; R is H,aliphatic, araliphatic, or aromatic; R is H or methyl; R R and R are H,alkyl, aryl, or aralkyl; R may also be carboalkoxy; R is alkyl orbenzyl; and m is 0, l, or 2. These dyestulfs are useful in the dyeing orprinting of fibrous materials, dyestuffs (11) particularly for thosebased on polymers or copolymers or acrylonitrile and dicyano-ethyleneand dyestulfs (I) particularly for those of aromatic polyesters. Processfor preparing the above dyestufi by combining A-NH with a couplingcomponent having the formula:

where all substituent groups have the above meanings. Process forpreparing the quaternary 's'alt azo dyestutf by reacting (I) withquaternizing agent R X.

The invention relates to valuable new azo dyestuffs which are free fromsulphonic acid groups and correspond to the general formula and to theirwater-soluble quaternary salts of the general formula In the Formulae Iand II, A denotes the radical of a diazo component, R is a non-ionicsubstituent, R is hydrogen or an aliphatic, araliphatic or aromaticradical, R is hydrogen or CH R and R are hydrogen or identical ordifferent alkyl, aryl or aralkyl radicals, R means hydrogen or identicalor difierent alkyl, aryl or aralkyl radicals or a carboalkoxy group, Ris an alkyl radical or a benzyl radical, the alkyl radicals in the abovegroups preferably containing 1-4 carbon atoms; In stands for the number0, 1 or 2 and X- for an anion. The radical A of the diazo component ispreferably a carbocyclic radical, such as a radical of the benzeneseries, or a heterocyclic radical, and the aryl radicals R R or R arepreferably phenyl, chlorophenyl, bromophenyl or alkyl (1 to 4 carbonatoms)-phenyl radicals.

Among the non-ionic substituents R the following should be speciallymentioned: halogen, such as Cl, Br; methyl and ethyl-sulphonyl radicals;lower alkyl radicals, such as methyl, ethyl and propyl or trifluoroalkylradicals; lower alkoxy radicals, such as methoxy and ethoxy radicals;and thioether radicals; the alkyl radicals preferably have 1-4 carbonatoms.

Aliphatic radicals R may contain further substituents, for example, thecyano group, an alkoxy group (1-4 carbon atoms), a hydroxyethyloxy groupor a carboalkoxy group, each of these groups standing in the ,8-positionof an ethyl radical.

The new azo dyestuffs of the Formula I are prepared by combining thediazonium compound of an amine of the formula A-NH (HI) in which A hasthe same meaning as above, with an azo component of the general formulain which R, R R R R R and m have the same meaning as above, selectingstarting components which are free from sulphonic acid groups.

The quaternary salts of the new azo dyestuffs, which correspond to thegeneral Formula II, are prepared, for example, by combining thediazonium compound of an amine of the formula A-NH (III) in which A hasthe same meaning as above, with an azo component of the formula (Rlm inwhich R, R R R R R and m have the same meaning as above and A stands fora radical of the benzene series, with quaternising agents R X, withquaternisation of the pyrazole ring. It is assumed that in this reactionthe alkyl or benzyl radical R becomes attached to the nitrogen atom 2 ofthe pyrazole ring of the dyestuffs of the general Formula VI.

The azo components of the general Formula IV to be used according to thepresent process are new. They are N-{fi-[pyrazolyl-(l)]-ethyl or-propyl}-anilines and their non-ionic substitution products andquaternary salts. These compounds are obtained, for example, Whenaniline or N-alkyl-anilines are reacted with the possibly substitutedbenzene-sulphonic acid esters or with the sulphuric acid semi-esters ofl-(B-hydroxyethyl)-pyrazoles, or with l-(B-chloroethyD- or1(/3-bromoethyl)-pyrazoles at an elevated temperature and, if desired,in an inert organic solvent, such as xylene, chlorobenzene,dichlorobenzene or methyl-naphthalene. The azo components can also beobtained by reacting N-alkyl-N-(B-hydrazinoethyl)-anilines withfi-diketo compounds. The quaternary salts of the Formula V are thenformed from the azo components of the general Formula IV by alkylation.The following alkylating agents can be used, for example: methylchloride, trimethyl-oxonium boron fluoride, dimethyl sulphate, diethylsulphate, ethyl bromide, p-toluene-sulphonic acid methyl, ethyl, propylor butyl ester.

Suitable azo components for the synthesis of the new dyestuffs are, forexample:

mourn CHzCHz-N CHzCHz-N CHzCH2O CzHa /CHiCHzCOO C211 N CHZCHZ-NCHzCHz-O-CHzCHzOH G ZCHz-N CHzCHz-N CHzCHrN COOCzH CHzCHz-N C Ha CHCHg-N NHCOCH:

CHzCHzCOOCzHs CHzCHzCN N om CHzCHz-N and the quaternary salts of thesecompounds, which carry the alkyl group or benzyl group on the nitrogenatom 2 of the pyrazole ring.

Suitable diazo components A-NH are, for example:

aniline,

2-chloroaniline,

3-chloroaniline,

4-chloroaniline,

Z-methylaniline,

3-methylaniline,

4-methylaniline,

2-ethylaniline,

3-ethylaniline,

4-ethylaniline,

2-nitroaniline,

3-nitroaniline,

4-nitroaniline, 2-chloro-4-nitroaniline, 2-chloro-3-nitroaniline,2-chloro-4,6-dinitroaniline, 2-brorno-4,6-dinitroaniline,2-nitr0-4-chloroaniline, 2-nitro-3-chloroaniline, 2,4-dinitroaniline,2,6-dichloro-4-nitroaniline, 2-cyano-4-nitroaniline, 2,4-dicyanoaniline,2,3-dichloroaniline, 2,4-dichloroaniline, 3,5-dichloroaniline,3,4-dichloroaniline, 2,4,5-triehloroaniline, pentachloroaniline,2-chloro-4-methylaniline, 2-methyl-4-chloroaniline, 4-aminobenzoic acid,

4-arninobenzoic acid ethyl ester, 3-nitro-4-amino-benzoic acid,3-nitro-4-aminobenzoic acid ethyl ester, 2-an1inobenzoic acid,3-chloro-4-cyanoaniline, 3-ch1oro-6-cyanoaniline, 4-aminobenzoic acidamide, 4-aminobenzoic acid dimethyl-arnide, 4-methylsulphonyl-aniline,Z-trifiuoromethyl-4-methylsulphonyl-aniline, 2-methylsulphonyl-aniline,2-ethylsulphonyl-4-nitroaniline, 2-chloro-4-ethy1sulphonyl-aniline,Z-aminobenzene-sulphonic acid phenyl ester, 4-methoxyaniline,

S-methoxyaniline, 2-nitro-4-rnethoxyaniline, 2-1nethoxy-4-nitroaniline,2-aminothiazole-( 1,3 2-amino-S-nitro-thiazole-( 1,32-amino-benzothiaZole-( 1,3 2-amino-6-ethoxybenzothiaz0le-( 1,3),Z-amino-6-methylsulphonylbenzothiazole- 1,3 5-amino-3phenyl-thiadiazole-1,2,4 B-aminopyridine, 8-aminoquinoline,

3-aminoindazole, 3-aminotriazole-(1,2,4).

Coupling of the starting components is carried out in known manner, forexample, in a neutral or weakly to strongly acidic aqueous medium.

If the dyestuffs according to the invention are prepared byquaternisation of dyestuffs of the general Formula VI, then thisreaction is expediently carried out by heating in an inert organicsolvent, for example, in hydrocarbons, such as benzene, toluene orXylene; halogenated hydrocarbons, such as carbon tetrachloride,tetrachloroethane, chloroform, chlorobenzene, o-dichlorobenzene;nitrated hydrocarbons, such as nitrobenzene or nitronaphthalene; or indimethyl formamide, acetonitrile or dimethyl sulphoxide, with the useof, preferably, equivalent amounts of alkylating agents, for example,with methyl chloride, methyl bromide, methyl iodide, ethyl bromide,benzyl chloride, trimethyl-oxonium boron fluoride, dimethyl sulphate,diethyl sulphate, p-toluene-sulphonic acid methyl, ethyl or butyl ester.

The resultant quaternised dyestuffs are sparingly soluble in thesolvents used and can be isolated by filtering off. If dimethylformamide, acetonitrile or dimethyl sulphoxide is used and thequaternised dyestuffs remain partially or completely dissolved, thenthey can be separated by dilution with water and addition ofwater-soluble salts, for example, sodium or potassium chloride.

The dyestuffs of the general Formula 11 prepared by coupling thediazonium compounds of amines of the Formula III with the couplingcomponents of Formula V, as well as those prepared by quaternisation ofdyestuffs of Formula VI, can be purified by dissolving them in water andprecipitating them by the addition of water-soluble salts, for example,sodium or potassium chloride.

The dyestuffs obtained by the present process contain the anionicradical X-, which is preferably the radical of a strong acid, forexample, of sulphuric acid or its semi esters or of an aryl-sulphonicacid or is a halogen atom. However, these anions can also be replacedwith the radicals of other acids, for example, of phosphoric acid,hydrofluoboric acid, formic acid, acetic acid, tartaric acid, lacticacid. The dyestuff salts can also be converted into double salts bymeans of inorganic salts, for example zinc chloride.

The water-insoluble dyestuffs of the general Formula I obtained by thepresent process are suitable for the dyeing and printing of fullysynthetic fibres, especially those of polyamides, cellulose esters andpolyesters and among the latter, in particular, of polyterephthalic acidglycol esters. The dyeings have good fastness properties. The dyestuffsof the general Formula II obtained by the present process arewater-soluble; they are eminently suitable for the dyeing and printingof fully synthetic fibres of polymers and copolymers of acrylonitrileand dicyanoethylene, fast dyeings being thus obtained. These dyestuffsEXAMPLE 1 16.2 parts 2,4-dichloroaniline are dissolved in parts of watercontaining 25 parts of concentrated hydrochloric acid and diazotised at0-5 C. with a solution of 6.9 parts sodium nitrite in 25 parts of water.After filtering, this diazonium salt solution is added to a solution of21.5 parts of a coupling component of the formula in 200 parts of 5%hydrochloric acid, and the coupling which starts immediately iscompleted after some time by the addition of sodium acetate. When thecoupling is completed, the dyestuff formed is filtered off, washed withwater until free from salt and acid, and dried. 37.2 parts of ayellow-orange powder are obtained. This dyestufI of the formula dyesfibres and fabrics made of polyamides in reddish yellow shades of goodgeneral fastness properties.

The coupling component used in the present example was prepared byreacting the p-toluene-sulphonic acid ester of 1-B-hydroxyethyl-pyrazoleat 140150 C. with N-ethyl-aniline (1 B hydroxyethyl pyrazole, preparedfrom fl-hydroxyethyl-hydrazine and 1,l,3,3-tetramethoxypropane, is aliquid and boils at 107-1085 C./10 mm. Hg). The coupling component thusobtained is a colourless liquid of 13.1. -120 C./0.08 mm. Hg.

Other valuable dyestuffs which are obtained by combining the' statedcoupling components with the stated diazo components, are listed inTable 1.

CzHs

CH CHzCHr-N I CH OH TABLE 1 Example No. Dlazo component Couplingcomponent Shade on polyamide 2 3,5-dlchloroaniline As in Example 1.Reddish yellow. 3 3,4-dichloroanillne.. do.. Do. 42,4,5-triehloroanlline... Do. 5.. Pentachloroanillne Do. 6..2-cyano-5-ehloroanlline Do 7.- 2,4-dieyanoaniline Yellowish red 8-..3,4-dicyanoaniline Do. 9.. 4-amlnobenzoic acid ethyl este Reddlsh yellow10 fi-ethoxy-2-aminobenzothlazole-(1,3) d Red 113-phenyl-5-amino-1,2,4-thiadlazole -d Red. 122trlfiuoromethyl-4-chloranillne .do Yellowish orange;

2 5 N 13 2,4-d1eh1oroanlline N\ CH3 R ddish yellow.-

CH OH -N 3,4.-dlchloroaniline Same as above Do.- 153,5-dichloroanlllne-..... ..do D0. 16 2,4,5-trichloroanilin Do. 17Pentaehloroanilln D0. 18--. 2-eyano-5-chloroaniline Do. 192,4-dieyanoaniline Yellowish red. 20-.- 3-4-dieyanoaniline Do. 214-aminobenzoie acid ethyl ester Reddish yellow. 226-et11oxy-2-aminobenzothiazole-(1,3) e 23 3-phenyl-5-amino-1,24-thiadiazole do Red. 24 2-trlfluoromethy1-4-chloroanil1n n Yellowlshorange.

can also be used for the dyeing and printing of tanned cellulosematerials, silk and leather.

In the following examples the parts are parts by weight.

The compound boils at 138 C./0.08 mm. Hg and has a melting point of 67C.

EXAMPLE 25 The diazonium salt solution prepared according to Example 1from 16.2 parts 2,4-dichloro-aniline is added to a solution of 22.9parts of a coupling component of the formula in 200 parts of 5%hydrochloric acid and the coupling, which starts immediately, iscompleted after some time by the addition of sodium acetate. Thedyestulf, which is isolated according to the instructions of Example 1,has the formula OzHt CHCH-N 1 TABLE 2 Example Coupling Shade on No.Diazo component component polyamide 26 3,5-dichloroani1ine As in Example25 Strongly reddish yellow 27 3,4-dlehloroaniline do Do. 282,4,5-trichloroaniline do Do 29 Pentachloroaniline do- 302-eyano-5-chloroaniline do Do. 31- 2,4-dicyan do. Red. 323,4-dicyanoaniline do Red. 33 i-anzlinobenzoio acid ethyl do Reddishester. yellow 34 fi-ethoxy-Z-aminobenzodo Red.

thiazle-(1,3). 85 3-phenyl-5-amino-1,2,4- do Red.

thiadiazole. 3G 2-trifiuoromethyl-4- do Orange.

chloroaniline.

EXAMPLE 37 17.7 parts 3-phenyl-5-amino-1,2,4-thiadiazole are dissolvedin 100 parts of 85% orthophosphoric acid while stirring, and thesolution is combined at 0 C. to 3 C. with a solution of 6.9 parts sodiumnitrite in 30 parts of concentrated sulphuric acid. Any excessnitrosyl-sulphuric acid which may be present is removed by the additionof 0.5 part urea. To this diazonium salt solution is added a solution of21.5 parts of a coupling component of the formula ornorn-N in 100 partsof glacial acetic acid. After this mixture has been stirred at 0-5 C.for 2 hours, it is stirred into 100 parts of water and bufiered withsodium acetate. The resultant dyestuif is thus precipitated incrystalline form and is filtered off, washed with water until free fromsalt and acid, and dried. 38.2 parts of the dyestufi of the formula\CH2CH2N/ are obtained.

When applied to fibres of polyterephthalic acid glycol ester by dyeingaccording to the usual dyeing methods (100 C, addition of carrier), thisdyestuff yields a scarlet-red dyeing of good fastness properties.

EXAMPLE 3 8 in 200 parts of 5% hydrochloric acid. The coupling givingthe azo dyestuif is completed after some stirring by the addition ofsodium acetate. The resultant dyestulf is isolated by filtering off,washed with water until free from salt and acid, and dried at C. forseveral hours. 38 parts of a dyestuff of the formula CzHs are obtainedin the form of a brown-red powder. This powder is introduced into 350parts of anhydrous chlorobenzene while stirring and the dyestulfsuspension so obtained is heated to C. while stirring. 12.5 partsdimethyl sulphate are then added dropwise at 100 C. within 30-40minutes. The temperature is subsequently raised to C. and maintained for'2 hours. The reaction mixture is then cooled and the dyestuif whichcrystallises out is filtered off. It is washed twice on a suction filterwith chlorobenzene and then dried. After drying, 49.9 parts of abrown-red water-soluble dyestuif of the formula are obtained.

This dyestuif dyes filaments or fabrics of polyacrylonitr1le from aWeakly acidic bath under the usual dyeing conditions in red shades ofvery good fastness properties.

EXAMPLE 39 The diazonium salt solution prepared according to Example 38from 17.3 parts 2-chloro-4-nitroaniline is added at 0 C., whilestirring, to a solution of 34.1 parts of a coupling component of theformula 1 1 12' in 350 parts of water. The coupling giving the azodyeare obtained. (In the course of working up, the major part stuff iscompleted by the addition of sodium acetate. The of the methosulphateanion initially present in the couresultant azo dyestuif is completelyseparated by the addipling component is replaced by the chloride anion.)tion of sodium chloride and filtered oil. The dyestuff is The dyestufi?so prepared has the same dyestulf cation dissolved in 400 parts of waterat 70 C. while still moist, as the dyestutf of Example 38 which wasprepared by a the solution is filtered and the dyestuff is precipitatedfrom ff rent me od, i by s bs quent q aternisation of the the filtrateby the addition of sodium chloride. After filfinished dy The dyeSt-uffalso y p y ryl i ri tering off, the dyestulf is dried at 60 C. 42.6-parts of a, fibres in red shades of very good fastness properties.

brown-red water-soluble dyestuff of the probable formula The couplingcomponent used in the present example 10 was prepared from the couplingcomponent of Example 38 and dimethyl sulphate in o-dichlorobenzene at120- Cl C2H5 E 125 C. It was used for coupling as crude product after N3distilling off the o-dichlorobenzene.

cl Other dyestuffs, which are obtained by reacting the CHQCHTN 15 statedazo dyestuff With the stated alkylating agent in xylene or chlorobenzeneat IOU-125 C., are listed in the following Table 3:

TABLE 3 Shade on poly- Example No. Azo dyestutl Alkylating agentacrylonitrile 40 /C2Hs Dirnethyl sulphate Reddish orange.

CHgCH2N 41 N do Bordeaux.

CHzCI-Iz-N 42 C1 p-Toluenesulphonic acid Orange-brown.

I 02H): methyl ester. OzN-N=N- N I CH CHr-N C1 43 CzH Dlothyl sulphateBordeaux.

oiN- N=N-N CH2CHz-N S 020113 44 Br Dimethyl sulphate Red.

CH CHz-N 45 C1 d0 Reddish C H Bordeaux. N OsN- N=N- N\ l GH2CH2N CH 46CzH do Ycllowish rod.

N oiN- N=N N I CH2CHZN CH3 47 N02 ...-...(10 Strongly z'Hs reddishorange. N N=N N\ CHzCHzN CH3 48 01 ...do Brick-rod.

C2115 N O2N- N=N- N\ A) ornam-- (31 H;

TABLE 3C0ntinued Shade on poly- Example N0. Azo dyestufi Alkylatmg agentacrylonitrile Cl C H 2 5 l 69 O N N=N N N do Bride-red.

CH2GH2 N Cl H3 1 N 70 om -N= N -CHa .--..do Bluish (J N Bordeaux.H2011:-

S 02 Ha &a

Cl C H 2 5 71 OzNN=N-N\ -----do Blmsh red.

61 CHzCHz-N Cl C H v 2 5 72 WQM A A4113 (B CH2CH2-N Cl C H 2 5 73 02N--N=N N -----do Strongly bluish CH3 red. C'HzCHz-N NHCOCHs Cl /CH2CH2CN 740113 H2CH2 CH2CH-N JJH: (1H3 C2115 1 R 76 02N CH3 0 ed:

I 0 t fth 01' tfth forml65 of 3 par s 0 e c up mg componen o e u a O2NN:N N

TABLE 3Continued Shade on poly- Example No. Azo dyestufi Alkylatingagent aerylonltrile o1 one-Q 77 OzN- N=NN N ...do Bluish red.

- CHa CHzCHrN Other valuable dyestuffs, which are obtained by com- 0 in250 parts of glacial acetic acid. The formation of the bining thediazonium compounds of the stated amines azo dyestuff is completed byportionwise adding sodium with the stated coupling components in theusual manner, acetate. The dyestuif formed is isolated by filtering, arelisted in the following Table 4:

TABLE 4 Shade on polyacrylo- Example No. DiazO component Couplingcomponent nltrile 78 Z-aminobenz0thlaz0Ie-(1,3) 02H CH3 Yellowish 5 lred. Q- HzCHz-N C S 0 Hz CH3 79 2-amln0-6'eth0xybenz0thlaz0le-(1,3) Sameas above-.. 80 2-amin0thiazole-(1,3) do 81-..2-amino-5-nitrothlazole-(1,3) ..do Violet. 82.5-amlno'3-phenyl-1,2,4-thiedlza0le .-d0 Red.

88 2-aminobenzothiazole-(1,3) (32HB 1H3 Red.

o) a CH2 Hr-N CHa SO H CHa 84 Zamiuothlazole-(LB) Same as above-Yellgwish re 85 3-amin0trlazole-(l,2,4) do Orange.

EXAMPLE 86 washed saltand acid-free with water and dried. The dye- 17.3parts of 2-chloro-4-nitroaniline are diazotised acstuff corresponds tothe formula cording to the method described in Example 38. The diazoniumsalt solution thus prepared is added to a solution 02H N CH:

cmorn-N Nnooom l CHzCHz-N NHCOCHa and dyes fibres frompolyethyleneglycolterephthalate bluish red shades having good fastnessproperties.

H The coupling component used in this example can be 75 prepared bynitrating the coupling component of Example 13 in concentrated sulphuricacid with nitrating acid, reduction of the nitro compound to the aminocompound and acylating the latter with acetic acid anhydride.

The following Table gives further diazo and coupling components whichcan be combined according to the method of this example yieldingvaluable monoazo dyestuifs which dye fibres from aromatic polyesters inthe shades indicated below.

oxy; R is hydrogen or methyl; R and R are selected from the groupconsisting of hydrogen, alkyl of 1-4 carbon atoms, phenyl, chlorophenyl,bromophenyl, and alkylphenyl wherein the alkyl group has 14 carbonatoms; R; is selected from the group consisting of hydrogen, alkyl of1-4 carbon atoms, phenyl, chlorophenyl, bromophenyl, alkylphenyl whereinthe alkyl group has 1-4 carbon atoms, and carboalkoxy wherein the alkoxygroup TABLE 5 Example Shade on No. Diazo component Azo componentpolyester 87 2-eyano-4-nitroanillne-, /CH Red Violet.

N OHzCHz-N NHCOOHa 88 3-phenyl-5-amino-1,2,4thiadiazole...-. Same asaaovo Red.- 89 2-bromo-4,6dtn1troaniline.-. do Bluish Bordeaux;

90 2-bromo-4,6-dinitroaniline 0 CH3 Blue.-

N 3 HaCHz-N NHCOCHQ We claim: has 1-4 carbon atoms; R is benzyl or analkyl of 1-4 (mm R2 R4 wherein A is a phenyl radical which isunsubstituted or substituted by a member of the group consisting ofchloro, bromo, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, nitro,cyano, carboxylic acid, carboxylic acid amide, carboxylic acid dimethylamide, phenyl, methyl sulfonyl, phenyl sulfonyl, ethoxy carbonyl, andphenoxy sulfonyl; R is a nonionic substituent selected from the groupconsisting of chloro, bromo, alkyl of 1-4 carbon atoms, sulphonylalkylof l-4 carbon atoms, alkoxy of 1-4 carbon atoms, trifluoroalkyl of 1-4carbon atoms, thioether, and aminocarboxymethyl; R is a radical selected from the group consisting of hydrogen, alkyl of 1-4 carbon atoms,benzyl, and ethyl substituted in the beta-position with cyano, alkoxy of1-4 carbon atoms, carboalkoxy of 1-4 carbon atoms, orbeta-hydroxyethcarbon atoms; m is 0, 1 or 2; and X is an anion.

2. A dyestutt of claim 1 corresponding to the formula:

3,329,669 7/1967 Sartori 26O158 CHARLES B. PARKER, Primary Examiner D.M. PAPUGA, Assistant Examiner US. Cl. X.-R.

